Process for producing polyether

ABSTRACT

The present invention provides a process for efficiently obtaining polyethers having its high degree of polymerization by easily polymerizing substituted epoxides which could hardly or could not be made so far to provide a high degree of polymerization. That is, a polyether is obtained by a process which comprises ring-opening-polymerizing at least one substituted epoxide, except for propylene oxide and epihalohydrin, in the presence of a rare earth metal compound represented by the formula (I) and a reducing compound: 
                 
 
Wherein M represents a rare earth element selected from Sc, Y and lanthanide, and L 1 , L 2  and L 3  are same as or different from each other and each of them represents an oxygen-binding ligand.

This application is a DIV of Ser. No. 10/082,059 filed Feb. 26, 2002 nowU.S. Pat. No. 6,800,723, which is a DIV of Ser. No. 09/622,592 filedSep. 13, 2000 now U.S. Pat. No. 6,417,323; which is a 371 ofPCT/JP99/00687 FILED Feb. 17, 1999.

TECHNICAL FIELD

The present invention relates to a process for producing a polyetherwhich has its high degree of polymerization and which is useful in thefield of cosmetics and in the field of chemical products and to a novelpolyether.

Up to now, in the ring-opening polymerization of a substituted epoxide,a molecular weight of the resultant product has been much decreased ingeneral owing to chain transfer originated from extraction of an atomfrom the substituent. With respect to propylene oxide and anepihalohydrin, the decrease in the polymerizability is not notablydecreased by way of exception. The molecular weight may reach millionsby selecting a catalyst. However, with the other substituted epoxide, apolyether having its high degree of polymerization could not be obtainedin good yield. This is notably observed in particular in the case of anepoxide having a bulky substituent, such as an epoxide having a longchain alkyl group or a silicone chain as a substituent and an epoxidehaving a highly electron-attractive fluoroalkyl chain as a substituent.That is, these could not be polymerized in good yield even by using acoordinated anionic catalyst, which is deemed in general to have a highactivity as a catalyst for polymerization of epoxide, such as a catalystcomprising organoaluminum-water-acetyl acetone and a catalyst comprisingorganozinc-water. Further, since an epoxide having a highly reactivehydroxyl group such as glycidol deactivates a coordinated anioniccatalyst, it could not be polymerized in high degree without protectingthe hydroxyl group.

In recent years, examples of using a composition containing a rare earthmetal compound as a catalyst for polymerization of ethylene oxide,propylene oxide or epichlorohydrin are seen in, for example, {circlearound (1)} Inorg. Chim. Acta, vol. 155, 263 (1989), {circle around (2)}Polymer J., vol. 22, 326 (1990) and {circle around (3)} Macromol. Chem.Phys., vol. 196, 2417 (1995). All of these tried to polymerize ethyleneoxide, propylene oxide or epichlorohydrin. It is described thatpolyethyleneoxide having its number average molecular weight of2,850,000 is obtained in {circle around (1)}, polyepichlorohydrin havingits viscosity average molecular weight (deemed to obtain a value beingclose to a weight average molecular weight) of 790,000 to 1,650,000 in{circle around (2)} and polypropylene oxide having its number averagemolecular weight of 70,000 to 980,000 (weight average molecular weightof 120,000 to 3,770,000) in {circle around (3)}. However, the degree ofpolymerization thereof is approximately the same as that of aconventional coordinated anionic catalyst. In consideration of the factthat when a substituted epoxide other than propylene oxide andepihalohydrin (hereinafter referred to as the substituted epoxide) waspolymerized using these conventional catalysts, a polyether having itshigh degree of polymerization could not be obtained. The rare earthmetal compound showing approximately the same performance as theconventional catalyst were not expected to be a useful catalyst in orderto obtain a polyether having its high degree of polymerization from thesubstituted epoxide.

DISCLOSURE OF INVENTION

The present invention is aimed to provide a process for efficientlyobtaining a polyether having its high degree of polymerization whichcomprises easily polymerizing a substituted epoxide, other thanpropylene oxide and epihalohydrin, being hardly or not able to bepolymerized in high degree, up to now.

The present invention provides a process for producing a polyether whichcomprises ring-opening-polymerizing a substituted epoxide, except forpropylene oxide and epihalohydrin, in the presence of a rare earth metalcompound represented by the formula (I) and a reducing compound andprovides a novel polyether obtained thereby:

wherein

M represents a rare earth element selected from Sc, Y and lanthanide,and

L¹, L² and L³ are same as or different from each other and each of themrepresents an oxygen-binding ligand.

MODE FOR CARRYING OUT THE INVENTION

(1) Substituted Epoxide

The substituted epoxide of the present invention means ethylene oxidehaving a substituent, and examples thereof are as follows.

(1-1) Compounds represented by the formula (II):

wherein

R¹ represents a hydrocarbon group which may have a substituent and whichhas 1 to 50 carbon atoms, represents an acyl group having 1 to 30 carbonatoms, represents an alkyl sulfonyl group having 1 to 30 carbon atoms oran aryl sulfonyl group having 6 to 30 carbon atoms or represents a grouprepresented by —(AO)_(n)—R².

Here, R² represents a hydrocarbon group, a fluoroalkyl group or afluoroalkenyl group, which may have a substituent and which has 1 to 30carbon atoms, or a fluoroaryl group, which may have a substituent andwhich has 6 to 30 carbon atoms, or represents a siloxysilyl group having1 to 500 silicon atoms. A represents an alkylene group having 2 or 3carbon atoms. n represents a number selected from 1 to 1,000.

Here, preferable examples of the hydrocarbon groups which may have asubstituent with respect of R¹ include an alkyl group or alkenyl grouphaving 1 to 42 carbon atoms and an aryl group having 6 to 42 carbonatoms. Examples of the substituent of the hydrocarbon group include ahydroxy group, an alkoxy group (having 1 to 30 carbon atoms), an aminogroup (a dimethyl amino group, a diethyl amino group or the like), anamide group, a trialkyl ammonium group, a dialkyl ammonium group, analkyl ammonium group, an ammonium group, an ester group, a carboxylgroup, an acyl group (having 1 to 30 carbon atoms), a silyl group, asiloxy group, a nitro group, an aryl sulfonyl group, a cyano group, aphosphonyl group (hereinafter referred to as “the substituent of thepresent invention”). An alkyl group in this case has 1 to 30 carbonatoms.

A preferable example of the acyl group may be an acyl group having 4 to22 carbon atoms in total. In this acyl group, a hydrocarbon group may bean alkenyl group. Further, R¹ may be a sulfonyl group having 1 to 30carbon atoms. A specific example thereof may be a benzenesulfonyl group,a toluenesulfonyl group or a nitrobenzenesulfonyl group.

(1-2) Compounds represented by the formula (III).

Wherein

R³ represents a fluoroalkyl group or fluoroalkenyl group, which may havea substituent and which has 1 to 30 carbon atoms, or a fluoroaryl groupwhich may have a substituent and which has 6 to 30 carbon atoms, and

a represents a number selected from 0 to 20.

a is preferably a number selected from 0 to 4. The R³ group ispreferably exemplified as trifluoromethyl, pentafluoroethyl,nonafluorobutyl, perfluorohexyl, perfluorooctyl, perfluorododecyl,perfluoro-3-methylbutyl, perfluoro-5-methylhexyl,perfluoro-7-methyloctyl, perfluoro-9-methyldecyl, 1,1-difluoromethyl,1,1,2,2-tetrafluoroethyl, 4H-octafluorobutyl, 5H-decafluoropentyl,6H-dodecafluorohexyl, 8H-hexadecafluorooctyl, 10H-icosafluorodecyl,trifluoroethenyl or perfluorophenyl. A preferable example of thesubstituent of R³ may preferably be “the substituent of the presentinvention” mentioned above.

In the substituted epoxide (III), a compound having a =0 and the R³group is a perfluoro group having 1 to 30 carbon atoms is morepreferable.

(1-3) Compounds represented by the formula (IV).

Wherein

all of plural R⁴s are same as or different from each other, and each ofplural R⁴s represents a hydrocarbon group which may have a substituentand which has 1 to 30 carbon atoms or represents a siloxy group having 1to 200 silicon atoms,

G represents an alkylene group, which may have a substituent and whichhas 1 to 20 carbon atoms, or an arylene group

b represents a number selected from 1 to 500 as an average value ofplural numbers or represents an integer of 1 to 20 as a single number,and

p represents a number selected from 0 and 1.

Here, when the R⁴ group is a hydrocarbon group which may have asubstituent and which has 1 to 30 carbon atoms, examples of thesubstituent include an ester group, an amide group, an amino group, ahydroxy group and a polyoxyalkylene group.

Preferable examples of the R⁴ group include a hydrocarbon group having 1to 10 carbon atoms and a linear or branched siloxy group having 1 to 100silicon atoms. More preferable examples include a methyl group, a butylgroup, a vinyl group and a phenyl group.

When the R⁴ group is a siloxy group, a group to combine with a siliconatom in the siloxy group may be a methyl group, a butyl group, a vinylgroup or a phenyl group.

In the (G)_(p) group, it may be preferably exemplified that p=0 or p=1and the G group is a alkylene group such as methylene group, ethylenegroup and trimethylene group, phenylene group or the like. In view ofeasiness of the synthesis, the methylene group or the trimethylene groupis especially preferable.

In the formula (IV), b represents a chain length of the siloxy group.The chain length may have a distribution or may be a single chainlength. Especially, when b is 1 to 20, it is possible that a polyetherhaving a siloxy chain comprising its single chain length is selectivelyobtained.

Properties of the polyether of the present invention, such as anappearance, an elastic modulus, a solubility in a solvent, vary greatlydepending on the value of b. The smaller value of b is, the moreremarkably this phenomenon is observed. Further, the smaller the valueof b is, the higher a hydrophilic property of the polyether is.

(1-4) Glycidol.

With respect to the substituted epoxide shown in (1-1) to (1-4), two ormore of these can be co-polymerized. Further, one or more of these andother epoxy compounds such as ethylene oxide, propylene oxide and/orepichlorohydrin can be co-polymerized. Still further, one or more ofthese and an anionic-polymerizable monomer can be co-polymerized.Examples of such a monomer include styrene, vinylnaphthalene,1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene,1,3-cyclohexadiene, vinyl pyridine, (meth)acrylic acid esters such asmethyl methacrylate, episulfides, 4-, 6- or 7-membered lactones, 5- or6-membered carbonates, lactams and cyclic silicones. More preferablemonomer is styrene, 1,3-butadiene, isoprene, methyl methacrylate,β-lactone and hexamethyl cyclotrisiloxane.

(2) Ring-opening polymerization of a substituted epoxide

In the rare earth metal compound represented by the formula (I), whichis used in the present invention, examples of M include Sc, Y, La, Ce,Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb and Lu. Among them, Sc,Y, La, Nd, Sm, Eu, Gd, Dy, Er, Yb or Lu is preferable in view of thepolymerization-activity and the economy.

Further, L¹, L² and L³ are oxygen-binding ligands. Examples thereof caninclude a methoxy group, an ethoxy group, an n-propoxy group, ani-propoxy group, a butoxy group, an allyloxy group, a methoxyethoxygroup, a phenoxy group, a 2-methoxypropoxy group, a trifluoroethoxygroup, a 2,4-pentanedionato group (acetyl acetonato group), atrifluoropentanedionato group, a hexafluoropentanedionato group, a6,6,7,7,8,8,8-heptafluoro-2,2-dimethyl-3,5-octanedionato group, a2,2,6,6-tetramethyl-3,5-heptanedionato group, a thienoyltrifluoroacetonato group, a furoyl trifluoroacetonato group, a benzoylacetonato group, a benzoyl trifluoroacetonato group, an acetato group, atrifluoroacetato group, a methyl acetoacetato group, an ethylacetoacetato group, a methyl (trimethyl)acetyl acetato group, a1,3-diphenyl-1,3-propanedionato group, a methyl sulfonate group, atrifluoromethyl sulfonate group, a dimethyl carbamate group, a diethylcarbamate group, a nitrite group, a hydroxamate group, and anoxygen-binding chelating agent such as an ethylenediamine tetraaceticacid, a diethylene triaminepentaacetic acid, an ethylenediaminetetrakismethylene sulfonic acid, a hydroxy ethylenediamine triaceticacid, nitrilotriacetic acid, and azomethene H. However, the ligand isnot limited by them.

Among them, an i-propoxy group, a 2,4-pentanedionato group (acetylacetonato group), a trifluoropentanedionato group, ahexafluoropentanedionato group, a 2,2,6,6-tetramethyl-3,5-heptanedionatogroup, an acetato group or a trifluoroacetato group is preferable inview of the polymerization-activity and the economy.

The rare earth metal compound can easily be synthesized by, for example,the reaction of a halide, oxide, hydroxide or nitrate of the rare earthmetal with the above-mentioned oxygen-binding ligand or a precursorcompound providing the ligand. Each of them may be used after it ispreviously synthesized and then purified. On the other hand, it may beused in the polymerization system while mixing the rare earth metalcompound and the above-mentioned oxygen-binding ligand or the precursorcompound providing the ligand.

Further, the rare earth metal compound can be used by being supported onan appropriate carrier if necessary. The type of the carrier is notparticularly limited. Any of inorganic oxide carriers, phyllosilicatessuch as clayey minerals, activated charcoals, metal chlorides, otherinorganic carriers and organic carriers may be used. Moreover, thesupporting method is not particularly limited, and a publicly knownmethod can be used at the option.

Moreover, the rare earth metal compound may contain an electron-donatingligand such as tetrahydrofuran, diethyl ether, dimethoxy ethane,tetramethyl ethylenediamine, triethyl phosphine.

The amount for use of the rare earth metal compound can be determined,as required, depending on the polymerizability of the said compound, thepolymerizable faculty and the amount for use of the substituted epoxide,the desired degree of polymerization and the total amount of thematerials which inhibit polymerization and which are present in thereaction system. In the case of the polymerization reaction in a highlypurified polymerization system, it is preferably between 0.000001 and 10equivalents, more preferably between 0.0001 and 1 equivalent, furtherpreferably between 0.0002 and 0.5 equivalent based on the number ofmoles of the substituted epoxide. When it is at least 0.000001equivalent, a high polymerization-activity can be obtained. Further,when it is at most 10 equivalents, formation of oligomers (low-molecularpolymers) can be inhibited.

The reducing compound used in the present invention may be any compoundso long as the compound has a reducibility for reducing the whole or apart of the trivalent rare earth metal compound represented by theformula (I) in order to generate a rare earth metal having quite a highpolymerization-activity. Examples thereof for use include (1) anorganoaluminum compound such as trimethyl aluminum, triethyl aluminumand triisobutyl aluminum; a two-component catalyst thereof; or athree-component catalyst obtained by adding an alcohol or a chelatingcompounds thereto; (2) an aluminum trialkoxide; (3) a dialkyl aluminumalkoxide; (4) a dialkyl aluminum hydride; (5) an alkyl aluminumdialkoxide; (6) methylaluminoxane.; (7) an organoaluminum sulfate; (8) atwo-component catalyst of an organozinc compound such as dimethyl zincand diethyl zinc with water; or a three-component catalyst obtained byadding a an alcohol or a chelating compound thereto; (9) a zincalkoxide; (10) an organolithium compound such as methyl lithium andbutyl lithium; and a mixture of one of them and water; and (11) anorganomagnesium compound such as dialkyl magnesiums and Grignardreagent; a mixture of one of them and water; and another organic andinorganic compound having its reducibility. Among them, theabove-mentioned catalyst (1), (6), (8) or (11) is preferable because ithas the appropriate reducibility.

Each of these reducing compounds may be used after it is previouslymixed with the rare earth metal compound and then reacted. On the otherhand, it may be used in the polymerization-system while being mixed withthe rare earth metal. By the way, when it is used after the previousmixing and reaction, it may be retained and aged at an appropriatetemperature in order to use it. This aging operation can furtherincrease the polymerization-activity.

The amount for use of the reducing compound can be determined, asrequired, depending on the reducibility and the type and the amount foruse of the rare earth metal compound. When the reducing compound is acompound containing a metal such as aluminum, zinc, lithium andmagnesium, the number of moles of the metal for use is preferablybetween 0.001 and 200 equivalents, more preferably between 0.01 and 100equivalents and especially preferably between 0.1 and 50 equivalents ascompared with the number of moles for use of the rare earth metal. Whenit is at least 0.001 equivalent, a high polymerization-activity can beobtained. Further, when it is at most 200 equivalents, formation ofoligomers (low-molecular polymers) can be inhibited.

When the present invention is being carried out, it is enough that thesubstituted epoxide is polymerized using the rare earth metal compoundrepresented by the formula (I) and the reducing compound. Thetemperature for the polymerization is desirable to be in the range of−78 to 220° C., especially −30 to 160° C. The polymerization of thesubstituted epoxide can be carried out in the absence of a solvent, whenthe substituted epoxide is in a molten state in the range of thetemperature for the polymerization. However, it is usually desirable tocarried out the polymerization in an inert solvent.

Examples of such a solvent include hydrocarbons such as benzene,toluene, xylene, ethyl benzene, n-pentane, n-hexane, n-heptane,isooctane and cyclohexane; ethers such as diethyl ether, dipropyl ether,dibutyl ether, tetrahydrofuran and dioxane; and halogenated hydrocarbonssuch as methylene chloride, chloroform and carbon tetrachloride; as wellas N,N-dimethyl sulfoxide and a mixture thereof. Usually, it is goodthat the solvent selected therefrom for polymerization is used aftersufficiently dehydration and deaeration.

Further, the polymerization of the substituted epoxide can also becarried out in a gaseous stream of the substituted epoxide, when thesubstituted epoxide is in a gaseous state in the range of thetemperature for the polymerization.

The polymerization reaction of the present invention is desirablycarried out under a condition in which oxygen is excluded. It isdesirably carried out under an atmosphere of an inert gas such asnitrogen, helium and argon; under a reduced pressure by deaeration;under a condition introduced with vapor of a solvent by deaeration; orin a gaseous stream of the substituted epoxide. The pressure forpolymerization is not particularly limited, and it may be any of normalpressure, reduced pressure or pressurization.

The polymerization reaction of the present invention can be carried outby an optional mixing method. The three members, i.e. the substitutedepoxide, the rare earth metal compound and the reducing compound, may bemixed at a time and used. To a system being prepared previously andcontaining one or two members of these, the remaining two or one membermay be added.

When the present invention is being carried out, one or more membersthereof can be used as the substituted epoxide. Further, each of thesecan be used in combination with the other epoxy compound, i.e. ethyleneoxide, propylene oxide epichlorohydrin and/or the like. When two or moresubstituted epoxy compounds are used, these may be mixed at a time andused. These can be introduced into the polymerization system one by oneto obtain a block polymer.

Moreover, when the present invention is being carried out, one or moreof the substituted epoxides can be used in combination with one or moreof anionic-polymerizable monomers other than epoxides. These may bemixed at a time and used or may be introduced into the polymerizationsystem one by one.

(3) Polyether

Examples of the polyether obtained in such a manner are as follows.(3-1) Polyether represented by the formula (V):

wherein

R⁵ represents a hydrocarbon group which has 8 to 50 carbon atoms andwhich may have a substituent, and

c represents a number being 150 and more on the average.

Here, the R⁵ is preferably an alkyl group or alkenyl group having 8 to42 carbon atoms. When it has a substituent, the substituent is “thesubstituent of the present invention”. The c is preferably between 200and 1,000,000.(3-2) Polyether represented by the formula (VI):

wherein

R⁶ represents a fluoroalkyl group having 2 to 30 carbon atoms,

J represents an alkylene group having 1 to 20 carbon atoms, and

d represents a number being 5 or more on the average.

Here, the R⁶group is preferably a perfluoroalkyl group, or a fluoroalkylgroup having 4 to 12 carbon atoms, more preferably a perfluoroalkylgroup having 4 to 12 carbon atoms. Further, a polyether wherein at leastone terminal group of the R⁶ groups is a —CF₂H group and the residueobtained by removing the —CF₂H group from the R⁶ group is aperfluoroalkylene group is also exemplified as a preferable example. Forexample, it is an ωH-perfluoroalkyl group having a hydrogen atom in itsterminal.

The J is preferably an alkylene group having 1 to 5 carbon atoms, morepreferably methylene group, ethylene group or trimethylene group. The dis preferably between 20 and 2,000,000, more preferably between 100 and1,000,000.(3-3) Polyether represented by the formula (VII):

wherein

R⁴, G, b and p represent the mean as defined in the formula (IV) in the(1-3) term, and

e represents a number being 5 or more on the average.

Here, preferable examples of the R⁴, G, b and p include those describedin the formula (IV) in the (1-3) term.

The e is preferably between 10 and 1,000,000.(3-4) Polyether represented by the formula (VIII):

wherein

X represents

in which R⁵ represents the mean as defined in the formula (V) in the(3-1) term, R⁶ and J represent the mean as defined in the formula (VI)in the (3-2) term, and R⁴, G, b and p represent the mean as defined inthe formula (IV) in the (1-3) term,

Y represents:

represents a group represented by X (provided that the case in which Xand Y are same as each other is excluded), or represents a grouporiginated from an anionic-polymerizable monomer other than thesubstituted epoxide, in which case Y may be plural types,

in which R⁷ represents a hydrocarbon group having 1 to 7 carbon atoms orrepresents a trialkyl (an alkyl group has 1 to 4 carbon atoms) silylgroup,

R⁸ represents a hydrogen atom or represents a hydrocarbon group orhalogen-substituted hydrocarbon group having 1 to 22 carbon atoms,

f represents a number being 150 or more when X is

or represents a number being 5 or more when X is the other group, and

g represents a number being 5 or more.

Here, the group originated from the anionic-polymerizable monomer refersto a group originated from an anionic-polymerizable monomer beingcopolymerizable with the substituted epoxide in any of the (1-1) to(1-4) term of the 1^(st) term.

The copolymer represented by the formula (VIII) is a system comprisingtwo- or more- component. In the formula (VIII), X and Y may be a randomtype or may be a block type.

The f is preferably between 150 and 1,000,000 and the g is preferablybetween 10 and 1,000,000.

BRIEF DESCRIPTION OF DRAWINGS

FIG. 1 is an NMR chart of a stearyl glycidyl ether polymer.

FIG. 2 is a DSC chart of a stearyl glycidyl ether polymer.

FIG. 3 is a dynamic viscoelasticity chart of a stearyl glycidyl etherpolymer.

FIG. 4 is a 200 MHz ¹H NMR chart of a polymer of Silicone Epoxide (1).

FIG. 5 is a GPC elution curve chart of a polymer of Silicone Epoxide(1).

FIG. 6 is a dynamic viscoelasticity chart of a silicone epoxide polymer.

FIG. 7 is an NMR chart of a copolymer of (stearyl glycidyl ether/octylether).

EXAMPLES

The preparation of a catalyst and the operation for polymerization werecarried out under an atmosphere of dry nitrogen. Each of varioussolvents was dried, then distilled and deaerated, therefore it was used.Commercially available and highly pure products of the rare earth metalcompound and the other inorganic compound were used as they were.Commercially available products of methylaluminoxane (hereinafterabbreviated as MAO), a solution (a solution used here is a toluenesolution and its concentration of aluminum is 10.2% by weight) anddiethyl zinc were used as they were.

Preparation Example 1 of Catalyst

0.9296 g of samarium triisopropoxide was basis-weighed, and 23.83 mL ofbenzene were added thereto. The resultant mixture was stirred. 5.06 mL(6 equivalents) of the MAO solution were added dropwise at roomtemperature while being stirred to prepare Catalyst A (Sm/Al (molarratio)=1/6).

Preparation Example 2 of Catalyst

0.5192 g of samarium tris(tetramethyl heptanedionate) was basis-weighed,and 7.20 mL of toluene were added thereto. The resultant mixture wasstirred while being heated. After the mixture was left to cool down toroom temperature, 0.22 mL (1 equivalent) of the MAO solution was addeddropwise while being stirred to prepare Catalyst B (Sm/Al (molarratio)=1/1).

Preparation Example 3 of Catalyst

0.3181 g of yttrium tris(tetramethyl heptanedionate) was basis-weighed,and 4.96 mL of toluene were added thereto. The resultant mixture wasstirred while being heated. After the mixture was left to cool down toroom temparature, 0.14 mL (1 equivalent) of the MAO solution was addeddropwise while being stirred to prepare Catalyst C (Y/Al (molarratio)=1/1).

Preparation Example 4 of Catalyst

0.3096 g of samarium tris(trifluoroacetate) was basis-weighed, and 9.70mL of toluene was added thereto. The resultant mixture was stirred whilebeing heated. After the mixture was left to cool down to roomtemperature, 0.30 mL (1 equivalent) of the MAO solution was addeddropwise while being stirred to prepare Catalyst D (Sm/Al (molarratio)=1/1).

Preparation Example 5 of Catalyst

0.6485 g of benzoyl trifluoroacetone was dissolved in 2 mL of 95%ethanol, and a matter which comprises 0.12 g of sodium hydroxide beingdissolved in 2 ml of distilled water was added thereto while beingstirred. After 20 minutes, a 50% ethanol solution (3 ml) of 0.4330 g oflanthanum nitrate with 6 hydrate per molecule thereof was added dropwiseto the obtained solution being pale yellow. A solid matter obtainedafter removal of the solvent by distillation was washed with water andwas then dried under reduced pressure at 70° C. for 24 hours.

9.11 mL of toluene were added to the above-obtained lanthanum compoundand the resultant mixture was stirred. 0.89 mL (3 equivalents) of theMAO solution was added dropwise thereto to prepare Catalyst E (La/Al(molar ratio)=1/3).

Preparation Example 6 of Catalyst

0.7002 g of samatrium tris(tetramethyl heptanedionate) wasbasis-weighed, and 7.73 mL of toluene were added thereto. The resultantmixture was stirred while being stirred.

0.20 mL of diethyl zinc was dissolved in 2.00 mL of toluene, and 0.073mL of glycerol was added thereto while being cooled with ice andstirred. The mixture was stirred at room temperature for 30 minutes andthen re-cooled with ice. The previous samarium solution was addedthereto. This was aged at 60° C. for 1 hour to obtain Catalyst F (Sm/Zn(molar ratio)=1/2).

Synthesis Example 1

1.74 g of tetraammonium tribromide were added to 50.0 g of2-(perfluorooctyl) ethanol and 20.0 g of epichlorohydrin under a gaseousstream of nitrogen, and the reaction was carried out in 65 ml of hexaneat 40° C. for 10 minutes. While the temperature of the resultantsolution was kept at 45° C. or less, 13 g of an aqueous solutioncontaining 48% of NaOH were added dropwise and the solution was furtherheat for 5 hours while being stirred. The reaction solution was left tocool down, then washed with deionized water and dried. This wasdistilled under reduced pressure to obtain3-(1H,1H,2H,2H-heptadecafluorodecyloxy)-1,2-epoxypropane.

Synthesis Example 2

144.5 mL of a hexane solution (1.556 M) of n-butyl lithium was added to360 mL of tetrahydrofuran (hereinafter referred to as THF) cooled withice under an atmosphere of nitrogen, and 25.0 mL of tetramethyl silanolwhich is dried, then distilled and purified was added dropwise. Afterthe resultant mixture was stirred at room temperature for 20 minutes, asolution of 100 g (2 equivalents) of hexamethyl cyclotrisiloxanedissolved previously in 260 mL of THF was added. The resultant solutionwas stirred at room temperature for 12 hours. The reaction solution wascooled with ice, and 122.5 mL (5 equivalents) of chlorodimethyl silanewere added dropwise. The mixed solution was further stirred at roomtemperature for 2 hours. After that, the solvent, the excesschlorodimethyl silane and the generated lithium chloride were removed.Just then, silicone hydride was obtained as a colorless liquid.According to the NMR analysis, the average number of silicon atomscontained in one molecule was 8.02.

From the above-obtained silicone hydride and an excess amount of allylglycidyl ether, Silicone Epoxide (1) having a dimethyl silicone chainwas obtained by a hydrosilylation reaction. This is provided withG=trimethylene, p=1, R⁴=methyl and b=7.02 in the formula (IV).

Synthesis Example 3

Silicone hydride having the low boiling point was removed at 75° C. and26.7 Pa from the silicone hydride obtained in the step of SynthesisExample 2. According to the NMR analysis, the average number of siliconatoms contained in one molecule was 8.72.

From the thus-obtained silicone hydride and an excess amount of allylglycidyl ether, Silicone Epoxide (2) having a dimethyl silicone chainwas obtained by a hydrosilylation reaction. This is provided withG=trimethylene, p=1, R⁴=methyl and b 7.72 in the formula (IV).

Synthesis Example 4

Silicone hydride was obtained in the same manner as in Synthesis Example2 except that 50 g (1 equivalent) of hexamethyl cyclotrisiloxane wasused instead of 100 g (2 equivalent). This was distilled under reducedpressure at 50° C. and 40 Pa to obtain 1H-undecamethyl pentasiloxane.

From this and an excess amount of allyl glycidyl ether, Silicone Epoxide(3) having a dimethyl silicone chain was obtained by a hydrosilylationreaction. This is silicone epoxide of a single composition and isprovided with G=trimethylene, p=1, R⁴=methyl and b=4.00 in the formula(IV).

Example 1 Poly(stearyl glycidyl ether): R⁵=Stearyl and c=430 in theFormula (V)

3.266 g of stearyl glycidyl ether were charged into a vessel purged withnitrogen, and 5.7 mL of toluene was added to make the ether dissolved.1.00 mL of Catalyst A was added thereto and then the vessel was closedwith the stopper. The polymerization was carried out at 130° C. withstirring.

After 10 hours, the vessel was opened, and the reaction solution wasadded to 100 mL of acetone containing a small amount of a dilutesolution of hydrogen chloride. A precipitated white solid was driedunder reduced pressure at 80° C. for 24 hours to obtain a polyether.Yield 85%.

1.00 g of this polyether was dissolved in 3 ml of chloroform, and thiswas added to 60 ml of acetone containing a small amount of a dilutesolution of hydrogen chloride. A precipitated white solid was driedunder reduced pressure at 80° C. for 24 hours to obtain a polyether as awhite solid.

According to the GPC analysis (130° C., o-dichlorobenzene, molecularweight calculated as polystyrene), the number average molecular weight(Mn) was 140,000 and the weight average molecular weight (Mw) was1,610,000. For the measurement, 150C model manufactured by Waters wasused and one piece of Shodex HT-806M and two pieces of Shodex HT-803manufactured by Showa Denko K.K. were used as columns. When themeasurement was carried out at 130° C. in the following Examples andComparative Examples, these conditions were employed.

An NMR (chloroform-d₁) chart is shown in FIG. 1. For the measurement,AC200P model manufactured by BRUKER was used.

According to the DSC (FIG. 2) measurement and the dynamicviscoelasticity measurement (FIG. 3), the polyether was a crystallinepolymer having melting point of crystalline side chain at 63° C. andbeing melted uniformly at 84° C. For the DSC measurement, DSC7manufactured by Perkinelmer was used. For the dynamic viscoelasticity,DVA-225 manufactured by ITK Corp. Ltd. was used.

Example 2 Poly(stearyl glycidyl ether): R⁵=Stearyl and c=640 in theFormula (V)

A polyether was obtained in the same manner as in Example 1 except thatthe polymerization was carried out at 100° C. for 24 hours. Yield 84%.White solid.

According to the GPC analysis (130° C.), Mn was 210,000 and Mw was2,350,000.

Example 3 Poly(stearyl glycidyl ether): R⁵=Stearyl and c=830 in theFormula (V)

A polyether was obtained in the same manner as in Example 1 except thatCatalyst B was used instead of Catalyst A. Yield 99%. White solid.

According to the GPC analysis (130° C.), Mn was 270,000 and Mw was2,200,000.

Example 4 Poly(lauryl glycidyl ether): R⁵=Lauryl and c=820 in theFormula (V)

A polyether was obtained in the same manner as in Example 1 except that2.422 g of lauryl glycidyl ether was used as the substituted epoxide andCatalyst B was used instead of Catalyst A. Yield 100%. White solid.According to the GPC analysis (130° C.), Mn was 200,000 and Mw was1,900,000.

Example 5 Poly(methyl glycidyl ether): R⁵=Methyl and c=2,700 in theFormula (V)

0.881 g of methyl glycidyl ether was charged into a vessel purged withnitrogen, and 8.1 mL of benzene were added to make the ether dissolved.1.00 mL of Catalyst C was added thereto and then the vessel was closedwith the stopper. The polymerization was carried out at 120° C. withstirring.

After 6 hours, the vessel was opened, and the reaction solution wasadded to 100 mL of a solvent which comprises diisopropyl ether mixedwith hexane (volume ratio of diisopropyl ether/hexane is 1/1) and whichcontains a small amount of a dilute solution of hydrogen chloride. Aprecipitated viscous matter was dried under reduced pressure at 80° C.for 24 hours to obtain a polyether. Yield 93%. Pale yellow and rubberysolid.

According to the GPC analysis (25° C., chloroform, calculated aspolystyrene), Mn was 240,000 and Mw was 1,610,000. For the measurement,a pump of CCPD model manufactured by Tosoh Corp. and a differentialrefractometer of SE-51 model manufactured by Showa Denko K.K. were used;and GMHHR-H, GMHXL, GMPWXL+GMPWXL and AC-G+GMHHR-H+GMHHR-H manufacturedby Tosoh Corp. were used as columns. When the measurement was carriedout at 25° C. in the following Examples, these conditions were employed.

According to the DSC and the dynamic viscoelasticity measurement, thepolyether was found to be amorphous at 25° C.

Example 6 Poly[3-(1H,1H,5H-octafluoropentyloxy)-1,2-epoxypropane]:R⁶=4H-octafluorobutyl, J=Methylene and d=1,430 in the Formula (VI)

7.00 g of samatrium tris(tetramethyl heptanedionate) were basis-weighed,450 ml of toluene were added, and the resultant mixture was dissolved byheating. After the solution was left to cool down to room temperature,17.83 mL of an MAO solution was added dropwise. After 20 minutes, 192.2g of 3-(1H,1H,5H-octafluoropentyloxy)-1,2-epoxypropane was added, andthe vessel was closed with the stopper. The polymerization was carriedout at 130° C. for 3 hours with being stirred and then the vessel wasopened. The polymerization was terminated with a dilute solution ofhydrogen chloride. After the product was cooled to room temperature, aprecipitated solid was collected by filtration, washed well with tolueneand then dried under reduced pressure. This was dissolved by heating in4 liters of ethanol and then filtered with a glass filter. The filtratewas charged into deionized water. The precipitated solid was dried underreduced pressure at 80° C. for 24 hours to obtain a colorless rubberysolid polyether. Yield 94%.

According to the GPC analysis (25° C., 50 mmoles/Liter of aceticacid/THF, calculated as polystyrene), Mn was 410,000 and Mw was1,420,000.

Example 7 Poly[3-(1H,1H,9H-hexadecafluorononyloxy)-1,2-epoxypropane]:R⁶=8H-hexadecafluorooctyl, J=Methylene and d=250 in the Formula (VI)

A solid polyether having pale yellow was obtained in the same manner asin Example 5 except that 244.1 g of3-(1H,1H,9H-hexadecafluorononyloxy)-1,2-epoxypropane was used as thesubstituted epoxide. Yield 93%.

According to the GPC analysis (25° C., 50 mmoles/Liter of aceticacid/THF, calculated as polystyrene), Mn was 120,000 and Mw was2,180,000.

Example 8Poly[3-(1H,1H,2H,2H-heptadecafluorodecyloxy)-1,2-epoxypropane]: in theFormula (VI), R⁶=perfluorooctyl, J=ethylene and d Being un-measurableBecause it is Insoluble in a Solvent

5.202 g of 3-(1H,1H,2H,2H-heptadecafluorodecyloxy)-1,2-epoxypropaneobtained in Synthesis Example 1 were charged into a vessel purged withnitrogen, and 5.7 mL of toluene were added to make it dissolved. 1.00 mLof Catalyst D was added thereto and then the vessel was closed withstopper. The polymerization was carried out at 130° C. for 3 hours withstirring. The vessel was opened and the polymerization was terminatedwith a dilute solution of hydrogen chloride. After the product wascooled to room temperature, a precipitated solid was collected byfiltration and washed with toluene. This was dried under reducedpressure at 80° C. for 24 hours to obtain a solid polyether being paleyellow. Yield 100%.

Example 9 Polyether Silicone: R⁴=Methyl, G=Trimethylene, p=1, b=7.02 ande≧28,000 in the Formula (VII)

7.089 g of Silicone Epoxide (1) obtained in Synthesis Example 2 werecharged into a vessel purged with nitrogen, and 9.9 mL of toluene wereadded to make the epoxide dissolved. 3.00 mL of Catalyst E was addedthereto and then the vessel was closed with the stopper. Thepolymerization was carried out at 130° C. with stirring.

After 6 hours, the vessel was opened, and the reaction solution wasadded to 500 mL of acetone containing a small amount of a dilutesolution of hydrogen chloride. A precipitated white gel was dried, thendissolved in chloroform, and charged into acetone containing a smallamount of a dilute solution of hydrogen chloride. The generated gel wasdried under reduced pressure at 80° C. for 24 hours. Yield 64%. Slightlyturbid-white soft solid. It was identified that the polyether wassoluble in a solvent such as dichloromethane, chloroform, hexane and hotTHF and did not have a crosslinked structure by a side reaction.

According to the 200 MHz ¹HNMR (chloroform-d₁) measurement, it wasidentified that the polyether had a silicone chain as a side chain (FIG.4).

According to the GPC analysis (25° C., chloroform, calculated aspolystyrene) using a set of columns with an exclusion limit of20,000,000, it was shown that a part of the polyether exceeded thisexclusion limit (FIG. 5).

Example 10 Polyether Silicone: R⁴=Methyl, G=Trimethylene, p=1, b=7.72and e≧2,600 in the Formula (VII)

The polymerization and the purification were carried out in the samemanner as in Example 9 using Catalyst B and 7.608 g of Silicone Epoxide(2) obtained in Synthesis Example 3. Yield 86%. The polyether was atransparent solid having its very soft fluidity. It was identified thatthe polyether was soluble in a solvent such as dichloromethane,chloroform, hexane and hot THF and did not have a crosslinked structureby a side reaction. According to the NMR (chloroform-d₁) measurement, itwas identified that the polyether had a silicone chain as a side chain(FIG. 4). Further, according to the GPC analysis (25° C., chloroform,calculated as polystyrene) using a set of columns with an exclusionlimit of 20,000,000, it was identified that a part of the polyetherexceeded this exclusion limit.

According to the DSC measurement, the polyether was amorphous and theglass transition point was −114.8° C. As the results (FIG. 6) of thedynamic viscoelasticity measurement (−180 to 100° C.) is shown, theelastic modulus at approximately 25° C. was in the order of 103 Pa andit was found to be quite soft. By the way, the elastic modulus atapproximately 25° C. of polyethylene glycol having its molecular weightof 5,000,000 is up to 10⁸ Pa and the elastic modulus at approximately25° C. of polydimethyl silicone [X-21-7784B (Mn=280,000) manufactured byShin-Etsu Silicone] is up to 10⁵ Pa.

Example 11 Polyether Silicone: R⁴=Methyl, G=Trimethylene, p=1 and b=4.00in the Formula (VII)

The polymerization was carried out for 24 hours in the same manner as inExample 9 using Catalyst F and 4.850 g of Silicone Epoxide (3) obtainedin Synthesis Example 4. The vessel was opened, and the reaction solutionwas added to 500 mL of acetone containing a small amount of a dilutesolution of hydrogen chloride. This was filtered with a membrane filterbeing made of Teflon® and having a pore size of 0.1 μm. The filtrate wasconcentrated, evaporated to dryness and further dried at 80° C. for 24hours. Then, a white brittle polymer having its film-like form wasobtained. Yield 34%. This polyether was easily powdered. It wasinsoluble in chloroform and dichloromethane.

According to the DSC measurement, the glass transition point of thepolyether was −91.6° C.

Further, according to the dynamic viscoelasticity measurement, theelastic modulus of the polymer at approximately room temperature was 10⁵Pa.

Example 12 Polyglycidol: the Degree of Polymerization 760

7.408 g of glycidol were charged into a vessel purged with nitrogen and38 mL of dioxane were added. 0.50 mL of Catalyst B was added thereto andthen the polymerization was carried out at 100° C. with stirring.

After 6 hours, a small amount of a dilute solution of hydrogen chloridewas added to the reaction solution to terminate the polymerization.Then, it was added to 100 mL of acetone. A white solid was filtered,then washed with isopropyl alcohol, and dried under reduced pressure at80° C. for 24 hours to obtain polyglycidol. Yield 99%.

5 g of the polyether was dissolved in 50 mL of deionized water, 0.05 gof hinokitiol was added, and the resultant mixture was stirred at 70° C.for 30 minutes. A precipitate was separated by filtration. Then, theobtained aqueous solution was washed with hexane, concentrated, and thenre-precipitated and purified with isopropyl alcohol. The precipitate wasdried, then re-dissolved in a small amount of water, and freeze-dried toobtain a transparent solid.

According to the GPC analysis (25° C., 0.2 M phosphoricacid/acetonitrile, calculated as polyethylene glycol)., Mn was 56,000and Mw was 66,000.

Example 13 Poly(stearyl glycidyl ether/octyl glycidyl ether)

f=190 and g=280 in the fomula (VIII).

50 mL of Catalyst B, 40.0 g of stearyl glycidyl ether (SGE) and 22.8 gof octyl glycidyl ether (OGE) were added to 210 ml of toluene, and avessel was closed. The polymerization was carried out at 130° C. for 24hours with stirring. The reaction solution was added to a large amountof acetone containing a small amount of a dilute solution of hydrogenchloride. A precipitated solid was dried under reduced pressure at 80°C. for 24 hours to obtain a poly(stearyl glycidyl ether/octyl glycidylether) copolymer. Pale yellow solid. Yield 75%.

According to the NMR (chloroform-d₁) analysis, the composition of thepolyether was (SGE)/(OGE)=62.3/37.7 (FIG. 7).

According to the DSC measurement, the melting point of the polyether was32.2° C.

According to the GPC analysis (130° C., o-dichlorobenzene, calculated aspolystyrene), Mn was 100,000 and Mw was 1,540,000.

Example 14 Poly(cetyl glycidyl ether/phenyl glycidyl ether)

f=410 and g=240 in the formula (VIII).

111 g of cetyl glycidyl ether (CGE) and 14.0 g of phenyl glycidyl ether(PGE) were co-polymerized in the same manner as in Example 13 to obtaina poly(cetyl glycidyl ether/phenyl glycidyl ether) copolymer. Paleyellow solid. Yield 86%.

According to the NMR (chloroform-d₁) analysis, the composition of thepolyether was (CGE)/(PGE)=77.2/22.8.

According to the GPC analysis (130° C., o-dichlorobenzene, calculated aspolystyrene), Mn was 160,000 and Mw was 1,930,000.

Example 15 Poly(stearyl glycidylether/3-(1H,1H,5H-octafluoropentyloxy)-1,2-epoxypropane)

J=methylene), f=420 and g=210 in the formula (VIII).

81.6 g of stearyl glycidyl ether (SGE) and 72.0 g of3-(1H,1H,5H-octafluoropentyloxy)-1,2-epoxypropane (OFPP) wereco-polymerized in the same manner as in Example 13. Pale yellow solid.Yield 67%.

According to the NMR (chloroform-d₁) analysis, the ratio of thepolyether in the composition was (SGE)/(OFPP)=69.1/30.9.

According to the GPC analysis (130° C., o-dichlorobenzene, calculated aspolystyrene), Mn was 200,000 and Mw was 3,600,000.

Example 16 Poly(stearyl glycidyl ether/ethylene oxide): in the GeneralFormula (VIII)

and f and g being unmeasurable because it is insoluble in a solvent.

19.4 g of stearyl glycidyl ether (SGE) and 19.4 g of ethylene oxide wereco-polymerized in the same manner as in Example 13 except that dioxanewas used as a solvent to obtain a colorless solid. Yield 53%.

According to the NMR (chloroform-d₁) analysis, the ratio of thepolyether in the composition was (SGE)/(ethylene oxide)=3.2/96.8.

Example 17 Poly(stearyl glycidyl ether/methyl methacrylate)

Y=—CH₂C(CH₃) (COOCH₃)—, f=350 and g=44 in the formula (VIII).

50 mL of Catalyst B and 32.6 g of stearyl glycidyl ether (SGE) wereadded to 210 mL of toluene, and a vessel was closed with the stopper.Then, the polymerization was carried out at 100° C. for 6 hours. Thevessel was left to be cool to 40° C., and then opened. 25.0 g of methylmethacrylate was added, and the vessel was closed with the stopper. Thepolymerization was further carried out at 120° C. for 6 hours. Thereaction solution was added to a large amount of acetone containing asmall amount of a dilute solution of hydrogen chloride. A precipitatedsolid was dried under reduced pressure at 80° C. for 24 hours to obtaina poly(stearyl glycidyl ether/methyl methacrylate) copolymer. Colorlesssolid. Yield 61%.

According to the NMR (chloroform) analyst, the ratio of the polyether inthe composition was (SGE)/(methyl methacrylate)=96.3/3.7.

According to the GPC analysis (130° C., o-dichlorobenzene, calculated aspolystyrene), Mn was 120,000 and Mw was 980,000.

Comparative Example 1

Stearyl glycidyl ether was polymerized in the same manner as in Example1 except that a 0.1 M toluene solution of a catalyst obtained by mixingtriethyl aluminum, water and acetyl acetone at a molar ratio of triethylaluminum/water/acetyl acetone being 1/0.5/1 was used instead of CatalystA. Yield 6%.

According to the GPC analysis (130° C., o-dichlorobenzene, calculated aspolystyrene), the polymer had Mn being 40,000 and Mw being 100,000.

Comparative Example 2

Stearyl glycidyl ether was polymerized in the same manner as in Example1 except that a 0.1 M toluene solution of a catalyst obtained by mixingtriethyl zinc and 1-methoxy-2-propanol at a molar ratio of triethylzinc/1-methoxy-2-propanol being 1/0.5 was used instead of Catalyst A.Yield 87%.

According to the GPC analysis (130° C., o-dichlorobenzene, calculated aspolystyrene), the polymer had Mn being 10,000 and Mw being 20,000.

Comparative Example 3

Stearyl glycidyl ether was polymerized in the same manner as in Example1 except that 0.75 g of cesium hydroxide was used instead of Catalyst Aand dimethoxyethane was used instead of toluene. After the operation ofre-precipitate, a solid was not obtained at all. Yield 0%.

Comparative Example 4

Silicone Epoxide (1) obtained in Synthesis Example 2 was polymerized inthe same manner as Example 12 except that a 0.1 M toluene solution of acatalyst obtained by mixing triethyl aluminum, water and acetyl acetoneat molar ratio of triethyl aluminum/water/acetyl acetone being 1/0.5/1was used instead of Catalyst G. After the operation of re-precipitate, asolid was not obtained at all. Yield 0%.

Comparative Example 5

Glycidol was polymerized in the same manner as Example 18 except that a0.1 M toluene solution of a catalyst obtained by mixing triethylaluminum, water and acetyl acetone at molar ratio of triethylaluminum/water/acetyl acetone being 1/0.5/1 was used instead of CatalystB. After the operation of re-precipitate, a solid was not obtained atall. Yield 0%.

Test Example

(Evaluation of a Gelability of Oils)

A gelability of aliphatic oils was not observed in the stearyl glycidylether polymer obtained by using the conventional catalyst for epoxidepolymerization (Comparative Examples 1 and 2, number average molecularweight 10,000 to 40,000). Meanwhile, poly(stearyl glycidyl ether) havingthe high molecular weight in the present invention was found to have itsgelability. The polymer in % by weight was added to various oils, andwas heated and dissolved at 100° C. for 10 minutes. The resultantmixture was left to be cool to 25° C., and the gelled condition of theoils was visually evaluated. ◯: gelled, Δ: quite sticky, ×: fluid.

TABLE 1 Liquid myristic Soybean paraffin acid oil Polymer of Example 1 ∘∘ ∘ Polymer of Example 2 ∘ ∘ ∘ Polymer of Example 3 ∘ ∘ ∘ Polymer ofExample 4 Δ Δ Δ Polymer of Example 5 x x x Polymer of ComparativeExample 1 x x x Polymer of Comparative Example 2 x x xIndustrial Applicability

According to the present invention, a polyether which has its highdegree of polymerization and which is useful in the field of cosmeticsand in the field of chemical products can be provided easily at goodefficiency.

1. A polyether represented by the formula (V):

wherein R⁵ represents a hydrocarbon group which may have a substituentand which has 8 to 50 carbon atoms, and c represents a number being 150to 1,000,000.
 2. A polyether represented by the formula (VI):

wherein R⁶ represents a fluoroalkyl group having 2 to 30 carbon atoms, Jrepresents an alkylene group having 1 to 20 carbon atoms, and drepresents a number being 5 to 2,000,000.
 3. The polyether as claimed inclaim 2, wherein the R⁶ group is a perfluoroalkyl group.
 4. Thepolyether as claimed in claim 2, wherein at least one terminal group ofthe R⁶ groups is a —CF₂H group and the residue obtained by removing the—CF₂H group from the R⁶ group is a perfluoroalkylene group.
 5. Thepolyether of claim 1, wherein R⁵ is an alkyl or alkenyl group.
 6. Thepolyether of claim 1, wherein R⁵ has 8 to 42 carbon atoms.
 7. Thepolyether of claim 1, wherein c is from 200 to 1,000,000.
 8. Thepolyether of claim 2, wherein R⁶ is a perfluoroalkyl group having 4 to12 carbon atoms.
 9. The polyether of claim 2, wherein J is an alkylenegroup having from 1 to 5 carbon atoms.
 10. The polyether of claim 2,wherein d is from 20 to 2,000,000.
 11. The polyether of claim 2, whereind is from 100 to 1,000,000.
 12. The polyether of claim 1, wherein R⁵ isan alkyl or alkenyl group having 8 to 50 carbon atoms and c is from 200to 1,000,000.